EP0159690A2 - Verfahren zum Kontrollieren des Sinterns von Metallpulvern - Google Patents

Verfahren zum Kontrollieren des Sinterns von Metallpulvern Download PDF

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Publication number
EP0159690A2
EP0159690A2 EP85104885A EP85104885A EP0159690A2 EP 0159690 A2 EP0159690 A2 EP 0159690A2 EP 85104885 A EP85104885 A EP 85104885A EP 85104885 A EP85104885 A EP 85104885A EP 0159690 A2 EP0159690 A2 EP 0159690A2
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EP
European Patent Office
Prior art keywords
sintering
metal particles
particles
metal
ceramic
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP85104885A
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English (en)
French (fr)
Other versions
EP0159690B1 (de
EP0159690A3 (en
Inventor
Lester Wynn Herron
Raj Navinchandra Master
Robert Wolff Nufer
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
International Business Machines Corp
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International Business Machines Corp
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Publication date
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Publication of EP0159690A2 publication Critical patent/EP0159690A2/de
Publication of EP0159690A3 publication Critical patent/EP0159690A3/en
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Publication of EP0159690B1 publication Critical patent/EP0159690B1/de
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    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/10—Sintering only
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/10—Sintering only
    • B22F3/1017—Multiple heating or additional steps
    • B22F3/1021—Removal of binder or filler
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
    • C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
    • C04B41/51—Metallising, e.g. infiltration of sintered ceramic preforms with molten metal
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
    • C04B41/81—Coating or impregnation
    • C04B41/85—Coating or impregnation with inorganic materials
    • C04B41/88—Metals
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/48—Manufacture or treatment of parts, e.g. containers, prior to assembly of the devices, using processes not provided for in a single one of the subgroups H01L21/06 - H01L21/326
    • H01L21/4814—Conductive parts
    • H01L21/4846—Leads on or in insulating or insulated substrates, e.g. metallisation
    • H01L21/4867—Applying pastes or inks, e.g. screen printing
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/09—Use of materials for the conductive, e.g. metallic pattern
    • H05K1/092—Dispersed materials, e.g. conductive pastes or inks

Definitions

  • the invention relates to a method of controlling the sintering temperature of metal particles. More particularly, it relates to a method of reducing the difference between the sintering onset temperature of the metal particles constituting a thick film conductor paste formed on a ceramic green sheet and the sintering onset temperature of the ceramic particles constituting the green sheet by preventing the sintering of the metal particles until a temperature close to the sintering temperature of the ceramic particles is reached.
  • sintering temperature and "sintering onset temperature” are herein used interchangeably. They refer to the lowest temperature at which agglomeration of the particles of a given medium occurs by thermal means.
  • (unfired) ceramic sheets are prepared from a composition consisting of a high melting point ceramic powdered material such as aluminum oxide, titanium oxide, barium oxide or calcium oxide, a lower melting point glass material such as lead silicate, borosilicate, magnesium aluminum silicate or soda-lime glass or a combination thereof, an organic resin binder material such as polyvinyl butyral, vinylchloride acetate co-polymer, polyvinyl alcohol, polyvinyl chloride, polystyrene or polyethylene, a plasticizer such as dibutyl phthalate, butyl benzyl phthalate or dioctylphthalate and a solvent such as trichloro ethylene, methyl ethyl ketone, methylalcohol, cyclohexanone or toluene.
  • a high melting point ceramic powdered material such as aluminum oxide, titanium oxide, barium oxide or calcium oxide
  • a lower melting point glass material such as lead silicate, borosilicate, magnesium
  • interlevel via holes at predetermined locations are punched in each green sheet followed by forming on the surface of each sheet a thick film electrical circuit pattern and filling the via holes thereon using a suitable conductive paste.
  • the conductive paste is typically a metallizing paste of copper or another non-refractory metal wherein the predominant component is the metal.
  • a sintering cycle involving relatively high sintering temperatures and long periods of time to volatilize the organic binding material and subsequently reform the ceramic particles into a dense and substantially impervious multilayer ceramic substrate.
  • a typical sintering cycle which is disclosed in U.S. Patent No. 4,234,367 is illustrated in Fig. 1.
  • the process consists of initially heating the laminated assembly in a non-oxidizing ambient such as pure nitrogen or nitrogen plus hydrogen at a slow rate until a carbon oxidation temperature of about 780°C is reached. Upon reaching the burn-out temperature the ambient is switched to an ambient of H 2/ H 2 0 at a volume ratio of about 10 -4 and these conditions are maintained for about 6-8 hours.
  • the hydrogen gas prevents oxidation of (i.e., serves as a reducing agent for) the metal particles constituting the thick conductor film and the water vapor enhances oxidation of the carbon and promotes the burn-out of the polymeric binder materials.
  • the H 2 /H 2 0 ambient is changed to nitrogen, with about 0.5-2.0 hour hold to remove entrapped or dissolved water with subsequent heating to a temperature of about 930-1000°C with about a 2 hour hold at this temperature for sintering and crystallization of the glass and ceramic particles constituting the green sheets.
  • the metal particles undergo sintering with attendant shrinkage of the thick film pattern during the initial phase of the sintering cycle whereas the ceramic and glass particles undergo sintering during the intermediate and final phases of the sintering cycle along with their characteristic shrinkage.
  • attention is focused on a pair of metal particles in physical contact with each other at a low, pre-sintering temperature. As the temperature is raised, the metal particles will initially form a neck at their mutual contact point due to inter-particle diffusion.
  • FIG. 2 A typical relative percentage shrinkage of metal and ceramic materials due to sintering is illustrated in Fig. 2. As shown in Fig. 2, not only are the sintering onset temperatures of metal and ceramic different giving rise to a sintering temperature differential AT, but also the sintering rates of these materials are quite diverse. AS is the difference in total shrinkage between the metal and ceramic materials. As a result of this disparity in shrinkage rates, the,multilayer ceramic substrate is prone to distortion introducing dimensional stability problems, i.e. proper contact of interlevel conductors is jeopardized.
  • Fig. 3 shows a fired unitary ceramic structure 10 having two via holes 11 and 12 containing interlevel conductors 13 and 14, respectively.
  • the separations in the via holes due to the pulling away of the metal discussed hereinabove are designated by numerals 15 and 16.
  • One method of delaying the sintering onset of the metal particles until at least the intermediate phase of the sintering cycle is to intersperse the metal particles in the thick film with a high melting point material such as molybdenum or aluminum oxide.
  • a high melting point material such as molybdenum or aluminum oxide.
  • the invention as claimed is intended to remedy this drawback. It solves the problem of how to reduce the difference in sintering temperatures of metal particles and glass-ceramic particles in the fabrication of a multilayer ceramic substrate without deleteriously affecting the electrical conductivity of the metal conductors.
  • the advantage of the invention is achieved by forming a barrier between the particles. Sintering is prevented until the barrier is removed typically by increasing the temperature in a suitable ambient.
  • the barrier is formed by coating the metal particles with a polymeric material such as polyvinyl butyral, polyvinyl formvar, polyvinyl alcohol, polyacrylonitrile, epoxies, urethanes, or cross-linked polyvinyl butyral. When subjected to relatively low temperatures using a non-oxidizing ambient the organic coating degrades due to the thermal energy supplied leaving a carbonaceous residue.
  • the residual carbon continues to act as a barrier preventing sintering of the metal particles until subjected to oxidation and further heating at which point it volatilizes permitting a coalescence of the metal particles into a dense mass.
  • Metals that can be conveniently inhibited from low temperature sintering by this method include copper, nickel, palladium, platinum, silver and gold and their alloys.
  • a dimensionally reproducible multilayer ceramic substrate may be fabricated by coating the powdered metal particles with an organic polymer material such as polyvinyl butyral before forming a metallized paste therefrom.
  • an organic polymer material such as polyvinyl butyral
  • via hole filling and circuit patterning on the ceramic green sheets is accomplished followed by the usual stacking and laminating of the green sheets.
  • the structure is then subjected to a conventional sintering cycle. Due to effective prevention of physical contact between the metal particles by the organic coating, the metal particles are inhibited from sintering even at temperatures exceeding their normal sintering temperature. As the firing temperature increases the organic coating slowly decomposes into a residual carbonaceous coating.
  • the carbonaceous coating continues to physically prevent the contact between metal particles until introduction of an oxidizing environment at which point the residual carbon oxidizes into gaseous byproducts permitting sintering of the metal particles along with the initiation of sintering of the glass-ceramic particles. Since the metal particles and the glass-ceramic particles sinter essentially simultaneously, the disparity between the shrinkage of the metal circuit pattern and the glass-ceramic structure will be minimal. Since the organic coating over the metal particles is fully oxidized excellent densification of the metal resulting in a high conductivity circuit pattern is achieved.
  • sintering of low melting point metal particles can be inhibited by forming a barrier between the metal particles until removal of the barrier typically by subjecting the powdered material to high temperatures and appropriate ambient conditions.
  • Metals that can be inhibited from sintering at their normal sintering temperature by this method include such high electrical conductivity metals as copper, nickel, palladium, platinum, gold and silver as well as their alloys.
  • Examples of the barrier that prevents low temperature sintering of the conductive material include organic polymeric materials such as polyvinyl butyral, polyvinyl alcohol, polyvinyl formvar, polyacrylonitrile, epoxies, urethanes and cross-linked polyvinyl butyral.
  • the barrier may be formed by coating the metal particles with the specified polymeric material.
  • One method of accomplishing the coating is starting with the metal in a powdered form, the powder is immersed in a solution consisting of the polymeric material and an evaporable solvent such as methyl alcohol. The powder is then removed from the solution and subjected to a drying process upon which a thin layer of the polymeric material will remain on the powder particles.
  • This barrier also serves to retard oxidation of the powder during storage.
  • the polymeric material-clad metal particles are combined in a conventional manner with suitable binders and vehicles forming a reactively bonded metallizing paste characterized by a low resistivity after sintering.
  • the vehicles and binders chosen must be those which may be given off at or below the sintering temperature of the ceramic so that only residual metallization remains after the process is completed.
  • the proportion of the organic and inorganic materials in the paste are adjusted to provide the proper rheology necessary for thick film screen printing.
  • One suitable vehicle in which the coated particles may be dispersed to form a paste thereof is a composition consisting of 20 % N-50 ethyl cellulose and 80 % butyl carbitol acetate which is disclosed in U.S. Patent No. 4,109,377 issued to L. A. Blazick and L. F. Miller and assigned to the present assignee. Reference is also made to this patent for details of preparing a metallizing paste using the conventional thick film milling processes.
  • the coated particles can also be formed into a paste by using commercially available techniques.
  • the metallizing paste is then deposited on a substrate material typically, a ceramic green sheet, by a conventional technique such as screen-printing, spraying, dipping, etc., in a desired pattern. Thereafter, the structure is fired to drive off the binders and to sinter the ceramic and metal particulates together.
  • One suitable firing schedule which enables co-sintering of the ceramic and metal particles at essentially the same temperature, namely the sintering temperature of the ceramic is heating the structure, as illustrated in Fig. 1, in a non-oxidizing ambient such as hydrogen or nitrogen or a combination thereof to a temperature of about 720-800°C exceeding the normal sintering temperature of the metal particles which is in the range of about 300-600°C. At these high temperatures, however, the polymeric coating over the metal particles transforms into a carbonaceous material.
  • Burn-out of the carbonaceous material occurs when an oxidizing ambient of hydrogen and H 2 0 in the ratio of H 2 /H 2 O of about 10 to 10 -6.5 is introduced. Thereafter an inert nitrogen plus hydrogen atmosphere is substituted for the oxidizing ambient and the structure is heated to a higher temperature of about 930-1000°C to complete sintering and crystallization of the glass-ceramic body.
  • a wide variety of structures can be fabricated which utilize co-sintering of a high sintering and maturing temperature glass-ceramic substrate material and a low sintering temperature thick film metal conductor forming composition formed on the substrate in their fabrication process.
  • the invention will be described in reference to the fabrication of a multi- layer ceramic substrate. More particularly, the invention will be described with reference to formation of a sintered glass-ceramic substrate containing multilevel interconnected thick-film circuit patterns of copper-based conductors. At the outset a copper paste for forming the required circuit patterns is prepared starting with a commercially available copper powder.
  • An alternative approach is start with a solution of a complex salt of copper, such as copper chloride, copper bromide, copper sulphate or copper nitrate and accomplish a reducing treatment using suitable catalysts, etc., to precipitate the copper out from the solution.
  • the copper powder is then immersed in a solution of an organic polymeric material such as polyvinyl butyral and an evaporable methyl alcohol solvent followed by subjecting the copper powder to a drying treatment to evaporate the solvent and leave a polyvinyl butyral coating over the individual copper particles in the powder.
  • Spray drying is another example of the drying treatment.
  • the weight percent of the polymeric coating on the copper particles is small, typically about 0.3-0.6.
  • the coated copper particles are subsequently formed into a conductor paste by combining with suitable binders, plasticizers, solvents, etc.
  • the coated copper particles are mixed with binder sqlvents such as those disclosed in the aforementioned U.S. patent to Blazick et al to form a copper paste having a desired viscosity.
  • the copper paste formed in this fashion is deposited by, for example, screen printing in patterns on required green sheets which form the component layers of the desired multilevel structure.
  • the via or feed- through holes punched in the green sheets for interlevel connection in the ultimate structure are also filled with the copper paste.
  • the laminate is fired to decompose the polymeric coating on the copper particles and other binders in the green sheets and to sinter the ceramic and metal particulates together using the sintering cycle depicted in Fig. 1.
  • the polyvinyl butyral which is present not only in the green sheet material but also in the coating over the copper particles degenerates at a steady rate at the low temperature and non-oxidizing ambient conditions corresponding to the initial phase of the sintering cycle (Fig. 1). Specifically, the predominant polyvinyl butyral degradation into carbon residue takes place below about 500°C followed by further relatively slow degradation thereafter. Since the carbonaceous coating formed over the copper particles due to polyvinyl butyral degradation will prevent establishment of a contact point between adjacent copper particles sintering of the copper particles will be inhibited.
  • This physical separation between the copper particles will continue until substitution of the H 2 /H 2 0 oxidizing ambient in place of the original non-oxidizing ambient at a desired temperature of about ; 780°C.
  • Switching to the oxidizing environment causes burn-off of the carbonaceous coating over the ceramic and copper particles. Once the carbon coating is oxidized and volatilized into gaseous byproducts, the copper particles physically come in contact with each other followed by the interparticle neck formation and ultimate coalescence in accordance with the normal sintering mechanism. This sintering atmosphere is maintained until a complete burn-off of not only the carbon residue over the copper particles but also that present in the green sheet material. Switching back to a non-oxidizing environment and further elevation of the temperature to the crystallization temperature of the glass particles in the green sheets will complete the glass particle coalescence and crystallization into a glass-ceramic structure.
  • the copper particles in the conductor paste and the glass-ceramic particles in the green sheet material sinter essentially simultaneously with minimal disparity between the shrinkage factors of the final copper conductor pattern and the glass-ceramic structure.
  • a benefit resulting from this is that the ceramic walls corresponding to the interlevel via holes closely embrace the metal conductor therein without leaving any room for formation of undesirable ceramic-metal separations along the walls.
  • This feature is illustrated in Fig. 5 where 20 designates a unitary ceramic substrate and 21 and 22 are metal conductors formed in via holes therein. Since the organic coating is fully oxidized into gaseous byproducts excellent copper densification is achieved resulting in a copper pattern having a high conductivity in the range 2-3 microohm-cm.
  • Fig. 7 is a micrograph in a view taken from the top of a glass-ceramic substrate having a matrix of interlevel via holes each accommodating a copper conductor therein.
  • the ceramic is formed snugly around the copper conductors.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Ceramic Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • General Physics & Mathematics (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Physics & Mathematics (AREA)
  • Production Of Multi-Layered Print Wiring Board (AREA)
  • Conductive Materials (AREA)
  • Powder Metallurgy (AREA)
  • Parts Printed On Printed Circuit Boards (AREA)
EP85104885A 1984-04-26 1985-04-23 Verfahren zum Kontrollieren des Sinterns von Metallpulvern Expired EP0159690B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US06/604,259 US4671928A (en) 1984-04-26 1984-04-26 Method of controlling the sintering of metal particles
US604259 1984-04-26

Publications (3)

Publication Number Publication Date
EP0159690A2 true EP0159690A2 (de) 1985-10-30
EP0159690A3 EP0159690A3 (en) 1987-10-21
EP0159690B1 EP0159690B1 (de) 1990-03-28

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EP85104885A Expired EP0159690B1 (de) 1984-04-26 1985-04-23 Verfahren zum Kontrollieren des Sinterns von Metallpulvern

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US (1) US4671928A (de)
EP (1) EP0159690B1 (de)
JP (1) JPS60230946A (de)
DE (1) DE3576793D1 (de)

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EP0267602A2 (de) * 1986-11-12 1988-05-18 International Business Machines Corporation Verfahren zur Herstellung einer Mehrschichtstruktur hoher Dichte aus Glaskeramik mit metallischen Leitern
EP0595745A2 (de) * 1992-10-28 1994-05-04 International Business Machines Corporation Verfahren zur Kontrolle des Verdichtungsverhaltens eines metallischen Anteils in einem keramischen Material

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US5543173A (en) * 1993-10-12 1996-08-06 Aluminum Company Of America Surface treating aluminum trihydrate powders with prehydrolized silane
US5348760A (en) * 1993-10-12 1994-09-20 Aluminum Company Of America Surface treated ceramic powders
DE19781541B4 (de) * 1996-11-27 2006-10-05 The Furukawa Electric Co., Ltd. Vorrichtung aus einem III-V-Verbindungshalbleiter und Verfahren zur Herstellung der Vorrichtung
JP3807257B2 (ja) * 2001-06-25 2006-08-09 松下電器産業株式会社 セラミック部品の製造方法
JP2006117959A (ja) * 2004-10-19 2006-05-11 Fukuda Metal Foil & Powder Co Ltd 電子材料用銅粉
DE102006047928A1 (de) * 2006-10-10 2008-04-17 Robert Bosch Gmbh Verfahren zur Herstellung mindestens einer porösen Schicht
KR102105402B1 (ko) * 2014-01-08 2020-04-29 삼성전기주식회사 다층 세라믹 기판 및 제조 방법
US9976058B2 (en) * 2015-05-29 2018-05-22 Palo Alto Research Center Incorporated High temperature seal compositions and methods of using same

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DE1665857A1 (de) * 1967-01-27 1971-04-15 Siemens Ag Verfahren zum Herstellen von festhaftenden loetfaehigen Metallueberzuegen auf Keramikteilen
US4186244A (en) * 1977-05-03 1980-01-29 Graham Magnetics Inc. Novel silver powder composition
US4234367A (en) * 1979-03-23 1980-11-18 International Business Machines Corporation Method of making multilayered glass-ceramic structures having an internal distribution of copper-based conductors

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0267602A2 (de) * 1986-11-12 1988-05-18 International Business Machines Corporation Verfahren zur Herstellung einer Mehrschichtstruktur hoher Dichte aus Glaskeramik mit metallischen Leitern
EP0267602A3 (de) * 1986-11-12 1990-08-01 International Business Machines Corporation Verfahren zur Herstellung einer Mehrschichtstruktur hoher Dichte aus Glaskeramik mit metallischen Leitern
EP0595745A2 (de) * 1992-10-28 1994-05-04 International Business Machines Corporation Verfahren zur Kontrolle des Verdichtungsverhaltens eines metallischen Anteils in einem keramischen Material
EP0595745A3 (de) * 1992-10-28 1994-11-23 Ibm Verfahren zur Kontrolle des Verdichtungsverhaltens eines metallischen Anteils in einem keramischen Material.

Also Published As

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US4671928A (en) 1987-06-09
EP0159690B1 (de) 1990-03-28
JPH0577197B2 (de) 1993-10-26
EP0159690A3 (en) 1987-10-21
DE3576793D1 (de) 1990-05-03
JPS60230946A (ja) 1985-11-16

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